Article comprising a fine-grained metallic material and a polymeric material

• US 20060135282A1
• Filed: 12/15/2005
• Published: 06/22/2006
• Est. Priority Date: 12/17/2004
• Status: Active Grant

• Current Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Original Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Inventors: McCrea, Jonathan, Tomantschger, Klaus, Panagiotopoulos, Konstantinos, Limoges, Dave, Jeong, Daehyun, Erb, Uwe, Palumbo, Gino, Brooks, Iain, Wang, Andrew
• Granted Patent: US 7,354,354 B2
• Time in Patent Office: Days
• US Class Current: 473/316
• CPC Class Codes: A01K 87/00 Fishing rods
• CPC Class Codes: A45B 9/00 Details
• CPC Class Codes: A63B 2209/00 Characteristics of used materials
• CPC Class Codes: A63B 2209/023 Long, oriented fibres, e.g. wound filaments, woven fabrics, mats
• CPC Class Codes: A63B 49/10 made of non-metallic materials, other than wood
• CPC Class Codes: A63B 49/12 made of metal
• CPC Class Codes: A63B 53/04 Heads
• CPC Class Codes: A63B 53/0416 Heads having an impact surface provided by a face insert
• CPC Class Codes: A63B 53/0466 wood-type
• CPC Class Codes: A63B 53/047 iron-type
• CPC Class Codes: A63B 53/10 Non-metallic shafts
• CPC Class Codes: A63B 53/12 Metallic shafts
• CPC Class Codes: A63B 59/00 Bats, rackets, or the like, not covered by groups A63B49/00 - A63B57/00
• CPC Class Codes: A63B 59/50 Substantially rod-shaped bats for hitting a ball in the air, e.g. for baseball
• CPC Class Codes: A63B 60/54 with means for damping vibrations
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 26/00 Coating not provided for in groups C23C2/00 - C23C24/00
• CPC Class Codes: C25D 15/02 Combined electrolytic and electrophoretic processes with charged materials
• CPC Class Codes: C25D 5/605 Surface topography of the layers, e.g. rough, dendritic or nodular layers
• CPC Class Codes: C25D 7/00 Electroplating characterised by the article coated
• CPC Class Codes: F42B 5/30 : of plastics , i.e. the cartridge-case tube is of plastics
• CPC Class Codes: Y02T 50/60 : Efficient propulsion technologies, e.g. for aircraft
• CPC Class Codes: Y10T 428/12049 : Nonmetal component
• CPC Class Codes: Y10T 428/12201 : Width or thickness variation or marginal cuts repeating longitudinally
• CPC Class Codes: Y10T 428/12569 : Synthetic resin
• CPC Class Codes: Y10T 428/1321 : Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/24612 : Composite web or sheet
• CPC Class Codes: Y10T 428/249941 : Fiber is on the surface of a polymeric matrix having no embedded portion
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31681 : Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• CPC Class Codes: Y10T 428/31685 : Natural source polyamide [e.g., casein, gelatin, etc.]
• CPC Class Codes: Y10T 428/31692 : Next to addition polymer from unsaturated monomers

Abstract

Lightweight articles comprising a polymeric material at least partially coated with a fine-grained metallic material are disclosed. The fine-grained metallic material has an average grain size of 2 nm to 5,000 nm, a thickness between 25 micron and 5 cm, and a hardness between 200 VHN and 3,000 VHN. The lightweight articles are strong and ductile and exhibit high coefficients of restitution and a high stiffness and are particularly suitable for a variety of applications including aerospace and automotive parts, sporting goods, and the like.

Claims

1. An article comprising

a) a permanent substrate comprising a polymeric material;

and

b) a fine-grained metallic material having an average grain size between 2 nm and 5,000 nm, a thickness between 25 micron and 5 cm, a hardness between 200 VHN and 3,000 VHN, said fine-grained metallic material covering at least a portion of said permanent substrate.

2. An article according to claim 1 wherein said surface of said permanent substrate to be covered by said fine-grained metallic material has an average surface roughness in the range of Ra=0.25 μ

m to Ra=25 μ

m.

3. An article according to claim 1 or 2, wherein said fine-grained metallic coating is selected from the group of:

i) a pure metal selected from the group consisting of Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W, Zn and Zr,

ii) an alloy containing at least two elements selected from Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W, Zn and Zr;

iii) a pure metal selected from the group of Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W, Zn and Zr and alloys containing at least two of these, further containing at least one element selected from B, C, Mo, Mn, P, S, Si, Pb, Pd, Rh, Ru, Sn and V;

iv) any of (i), (ii) or (iii) where said metallic coating also contains particulate additions in the volume fraction between 0 and 95% by volume.

4. An article according to claim 3, wherein said metallic coating also contains particulate addition and said particulate addition is one or more materials selected from the group of metals (Ag, Al, Cu, In, Mg, Si, Sn, Pt, Ti, V, W, Zn);

metal oxides (Ag₂O, Al₂O₃, SiO₂, SnO₂,TiO₂, ZnO);

nitrides of Al, B, Si and Ti, carbides of B, Cr, Bi, Si, Ti, W;

MoS₂;

carbon (carbon nanotubes, diamond, graphite, graphite fibers);

ceramics, glass; and

polymer materials (PTFE, PVC, PE, PP, ABS, epoxy resins).

5. An article according to claim 1, wherein said permanent substrate is a polymeric material selected from the group of filled or unfilled polymer materials selected from the group of epoxy resin composites, polyamide, glass filled polyamide, polyester, polythalamide, polypropylene, polycarbonate, polyvinyl chloride (PVC), thermoplastic polyolefins (TPOs), polycarbonate and acrylonitrile-butadiene-styrene (ABS) optionally containing fillers selected from the group of glass, glass fibers, carbon, carbon nanotubes, graphite, graphite fibers, metals, metal alloys, ceramics and mineral fillers such as talc, calcium silicate, silica, calcium carbonate, alumina, titanium oxide, ferrite, and mixed silicates.

6. An article according to claim 1 wherein the fine-grained metallic layer is deposited by electrodeposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and cold spraying techniques including kinetic metallization.

7. An article according to claim 1 wherein said fine-grained metallic coating has a yield strength of at least 300 MPa.

8. An article according to claim 1 containing an intermediate conductive layer between said metallic material and said polymeric substrate.

9. An article according to claim 8, where the intermediate conductive layer comprises a metallic layer constituted of Ag, Ni or Cu or a combination of any two or all of these, and where the intermediate conductive layer is deposited by electroless deposition, sputtering, thermal spraying, chemical vapor deposition, chemical reduction spray, physical vapor deposition or by any two or more of these.

10. An article according to claim 8 where the intermediate conductive layer comprises polymeric material with conductive particulates therein.

11. An article according to claim 10 where the intermediate conductive layer is a conductive paint or a conductive epoxy.

12. An article according to claim 10 where the conductive particulates are composed of or contain Ag, Ni or Cu or graphite or other conductive carbon or a combination of two or more thereof.

13. An article according to claim 8, comprising a polymeric adhesive material.

14. An article according to any one of claims 1 to 13, wherein said article is a component or part of an automotive, aerospace, sporting equipment, manufacturing or industry application.

15. An article according to claim 14 selected from the group consisting of golf club shafts and golf club heads, fishing rods, arrows, hockey sticks, baseball bats, tennis racquets, skate blades, snowboards, bicycle frames, ammunition casings, grille guards, brake pedals and running boards.

16. A golf club shaft according to claim 15 made of a graphite-containing polymeric material, wherein said fine-grained metallic material contains at least one metal selected from the group of Ni, Co and Fe.

17. An ammunition casing according to claim 15 wherein said fine-grained metallic material contains at least one metal selected from the group of Ni, Co and Fe.

18. An article according to any one of claims 1 to 11, wherein said article has a tubular structure and said fine-grained metallic material extends over at least part of the inner or outer surface of said tubular structure.

19. An article according to claim 18 selected from the group of golf club shaft, arrow shaft, cartridge casing, baseball bat, fishing rod, ski poles, hiking poles and bicycle parts.

20. An article according to claim 18 wherein said substrate comprises a polymeric material containing filler selected from the group consisting of graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes.

21. An article according to claim 18, having a fine-grained metallic coating with a hardness of greater than 500 VHN and a ratio of wall thickness to grain size of greater than 10.

22. An article according to claim 1 having an fine-grained metallic material coating on a substrate containing graphite/carbon fibers embedded in epoxy, wherein the weight of the fine-grained metallic material is between 5 and 95% of the total weight of the article.

23. An article according to claim 1, wherein said fine-grained metallic material is a Ni, Co or Fe based alloy and the substrate comprises graphite/carbon fibers embedded in epoxy resin.

24. An article according to claim 22 or 23, wherein said article is a golf club shaft, arrow shaft, ammunition cartridge casing, baseball bat, fishing rod, a ski pole, a hiking pole;

a mold, mold component or tooling part;

or an automotive or bicycle part.

25. An article according to any one of claims 1 to 7, wherein said fine-grained metallic material is an electroformed metallic plate or tape which, after forming, is applied to the polymeric substrate.

26. An article according to any one of claims 1 to 7, wherein said fine-grained metallic material after formation, is strengthened by a heat treatment.

27. An article comprising a fine grained metal coated polymer composite having a yield strength of at least 25 MPa wherein

i. the weight of the fine-grained coating is between 5% and 95% of the total weight of the article;

ii. said article containing the fine-grained metallic coating has a torsional or bending stiffness per unit weight improved by at least about 5% when compared to the torque or moment of the same article not containing the metallic coating.

28. An article according to claim 27, wherein said fine-grained metallic coating layer covers at least part of the inner or outer surface of the article.

29. An article according to claim 27, wherein said article is a golf club shaft, an ammunition casing, an automotive grille guard or an automotive running board bracket.

30. An article comprising a polymeric material, the surface of which is at least partially coated with a fine-grained metallic material having a grain size of between 2 and 5,000 nm and a yield strength of at least 200 MPa.

31. An article according to claim 30 wherein the surface roughness of said polymeric material which is coated by said fine-grained metallic material is in the range of Ra=0.4 μ

m to Ra=5 μ

m.

32. An article according to claim 30 wherein the outside of said article is coated with said fine-grained metal to thickness of between about 25 μ

m to about 5 cm.

33. An article according to claim 30 wherein said polymeric material is reinforced.

34. An article according to claim 30 containing a metallized layer between said polymeric material and said fine-grained metallic layer.